Extraction of oxygenated compounds from oils with aqueous salt solutions



' containing compounds produced in operation may be a major product Patented June 15, 1954 2,681,356 ICE OXYGENATED COM- OILS WITH AQUEOUS SALT SOLUTIONS Herbert K. Wiese, Cranford, N. J., assignor to EXTRACTION OF POUNDS FROM Standard Oil Development poration of Delaware No Drawing. Application Company, a cor- June 3, 1948,

Serial No. 30,968

1 Claim.

This invention relates to a process for the extraction of organic oxygenated compounds, particularly alcohols, from their solutions in hydrocarbons. The invention is also concernecl'with a process for the extraction of organic oxygenated compounds from hydrczarbon oils with the simultaneous hydrolysis of the esters present among the oxygenated compounds. More specifically, the invention is concerned with a process for extracting organic oxygenated compounds, particularly alcohols, from hydrocarbons by contact with aqueous salt solutions of organic acids of 3 to about 12 carbon atoms.

It is an object of this invention, therefore, to set forth a process for the separation of organic oxygenated compounds, i. e., alcohols, acids, esters, ketones, aldehydes etc., but particularly alcohols from hydrocarbon oils containing them.

It is another object of this invention to set forth an extraction process for the separation of organic oxygenated compounds, particularly alcohols, from hydrocarbon oils during which the esters present in the hydrocarbon oils are hydrolyzed to alcohols and acids which are simultaneously extracted by the hydrolyzing medium.

These and other objects of the invention may be accomplished according to the process which will be set forth below.

Various processes are known to the art in which a mixture of hydrocarbons and organic oxygen-containing compounds are produced. Some of these processes are the low temperature carbonization of coal, peat and similar materials, destructive hydrogenation of coals, wood, shales, etc. Numerous oxidation processes, particular- 1y oxidation of petroleum oil fraction such as is described in Ellis Chemistry of Petroleum Derivatives, vol. 1, chapter 36, pages 830 to 845, also yield mixtures of oxygenated compounds and hydrocarbons. This invention is particularly applicable to products obtained from aprocess whereby hydrogen and oxides of carbon are reacted in the presence of a catalyst to produce synthetic hydrocarbons, water and numerous organic oxygenated compounds. The oxygenthis synthesis or a relatively small by-product depending upon the operating conditions. These oxygenated materials which are extremely valuable as chemicals, consist of a mixture of alcohols, acids, aldehydes, ketones and esters, and are difficult to separate from the hydrocarbon oil, because, first, they are so numerous, secondly, they boil within substantially the same range as the hydrocarbon oils and, thirdly, they often form azeotropes with each other and with the hydrocarbon oils.

Normally, when the products of the abovedescribed synthesis operation are condensed and allowed to settle the condensate separates into 'a di-phase system, that is, an upper oil layer comprising substantially hydrocarbons and hydrocarbon-soluble oxygen containing materials and a lower water phase comprising substantially water and water-soluble oxygen-containing materials. The oxygen-containing organic compounds formed in the synthesis operation range from very low molecular weight compounds to very high molecular weight compounds and, therefore, find themselves distributed throughout the oil phase and the water phase depending on their solubilities in these respective phases. In general, it can be said that the bulk of the organic oxygen-containing compounds of one to four carbon atoms will enter the aqueous phase while the bulk of the compounds containing five carbon atoms and more per moleculewill be found in the oil layer, although it should be borne in mind that the separation of materials into their respective phases is oftentimes not cleancut and depends to a large extent upon the conditions involved and the overall composition of the materials in the condensate.

The process of this invention is concerned with the separation and recovery of organic oxygencontaining compounds such as alcohols, acids, ketones, aldehydes etc. from their solutions in hydrocarbon oils. The invention is also concerned with the simultaneous hydrolysis of any esters in the solution to the corresponding alcohols and acids which become extracted by the hydrolyzing medium. The invention is particularly applicable to the products of the previously mentioned hydrocarbon synthesis reaction products resulting from the catalytic hydrogenation of oxides of carbon.

According to one modification of the process of this invention organic oxygen-containing compounds such as alcohols, acids, carbonyls etc. are extracted and any esters are hydrolyzed by contacting the hydrocarbon solution of the oxy-compounds with an aqueous solution of a salt of an organic carboxylic acid containing 3 to about 12 carbon atoms per molecule. The process is preferably carried out ina countercurrent operation and preferably in a liquidliquid operation whereby the oxy-compounds dissolve in the aqueous salt solution forming an extract phase, while the hydrocarbons remain undissolved and constitute the rafiinate phase.

The material subjected to extraction, according to the terms of this invention, is complex in nature. It is composed of hydrocarbons including paraffins, olefins and in some cases, small amounts of aromatics. In addition, it contains anywhere up to about 50% or more of oxygencontaining materials, particularly of high molecular weight such as those set out above. In caseswhere the material is derived from the hydrocarbon synthesis operation, the oil will have dissolved in it alcohols, acids, aldehydes, ketones and esters. The esters predominate among the high boiling compounds, particularly that fraction boiling above 350 F. whilecarbonyl .com-

pounds, that is, aldehydes and ketones, acids.

ing analytical distillation temperatures due 1111- doubtedly to the fact that'they undergo 'ester'ir fication reactions during such distillation treatments. The oxygen content of the hydrocarbon.

oils resulting from the synthesis operationgen' erally runs from one weight percent toabout 10 wt. percent.

v.Whenesters are present in such mixtures .of .oxy-compounds they tend to solubilize the other oxy-compounds in the hydrocarbon oils .and make their extraction more diihcult. Solvent extraction processes developed to date permit the quantitative removal of all oxy-compounds .irom solutionsin hydrocarbons with the exception of esters. These processes, or" course, permit the removal .of some esters, butby no .means 'islthe .esterremova1 quantitative. These esters are valuable products themselves and are even more .valua'blefrom the point of view of the alcohols and acids obtainable therefrom. It is extremely important, therefore, that the esters .be recov- Sodium formate and sodium acetate are inferior ,to water as an extracting medium.

The concentration of salt solution employed depends upon-the character of the material which is-being extracted from the hydrocarbon solution. For example, a lower concentration -of salt in the aqueous than 'when" extracting -10 solution could be empropyl alcohol from oil hexyl or octyl alcohol from, the -;.oil. Generally, salt solutions in the ployed when extracting range of 5 wt. percent to 75 wt. percent, preferably about wt. percent to 60 wt. percent are .ered as such or as their hydrolysis products, and

furthermore, thatthe raflinate be freed of such compounds in order .that it may be used as a gasoline .or. other products, which will not tolerate. the presence of such ester contaminants. The salts employed in the process of this invention are derived from a combination oi at least .one organic acid'of. the molecular weight prescribed and an inorganic base, e. g., sodium hydroxide, or, from a combination of an. organic .acidand an organic base, such as the aminesorsultonium .hydroxide. The salt solution may be prepared by adding a .pure. organic acid or mixture. of pure organic acids to an-.aqueous .base to produce. the. desired extractant. However, it is preferred in this invention to prepare ,thasalts'olution by contacting an aqueous solution ofthe base of desired concentration. with a.hydrocarbon synthesisproduct fraction, either oil layer or water layer or both, containing the desired acid or acids.

, desires toextract the oxygenated. compounds The resulting salt .solution is then employed to extract thev oxygenated from a hydrocarbon synthesis oil gasoline. fraction, a part of the. gasoline fraction is first con- ,,tacted with anaqueous solution. of sodium hy- .droxide until all or a part otthe .baseis .neutralized. The aqueous salt solution so produced can then be employed to extract oxygenated compounds from the gasoline fraction either in batch or countercurrentoperation at room temperature or at elevated temperatures. other hydrocarbon fractions containing, for example,

"C10 to C12 acids, may likewise be treated with an appropriate base and the resulting salt solution of these acids employed as the extractant. The

' hydrocarbon synthesis water layer contains con- 'siderable amounts of the lower aliphatic carboxylic acids, e. g., C3 to Ccand is an .excellent source of acids for the production of organic "salts which may be employed according to this invention. 1 Typical salts, therefore, whichmay .be employed are sodium or potassium "propionate, sodium or potassium but-yrate etc. ormixtures thereof, or other salts of organicacids con- .taining 3 to about 12 carbon atoms per molecule.

, .500 to.1,000 lbs.p. s. i.,is.employed.

employed.

The temperature at which the. extraction is carried out may'vary from about room. temperature' to the critical temperature of the salt .solution being employed. 'Room temperature is completely satisfactory for carrying. out the simple extraction process. However, if ,it' .is .-.desired tojsimultaneously hydrolyze the esters present inthe .feed to the extraction, process, higher temperatures in the neighborhood of 100 to'.350'C., pref.erably1250 to 350 C. areemployed, depending upon the ester content .oithe .originalflfeed. Temperature has a marked effect upon the rate of hydrolysis of esters. An acid-free gasoline fraction resulting from a .hydrocarbon synthesis run, and. containing 2.0 wt. .percent..-esters as C6 testers was subjected .toan aqueous" solution containing mixed. sodiumsalts of organic acids as thehydrolyzing medium... 'At .a contact time oi ten minutes. at .200..C.',.25.m'ol percent of the esters were hydrolyzed,,whi-le. at 250". C. andthe same contact time 52.5 mol percent of the esters were hydrolyzed. Organic acids themselves, causedno appreciable ..hy drolysis.

The pressure employed in the extraction process will bethat necessary tokeep the-materials in the liquid phase and will, .of. course, depend upon the volatility of the feed andthesolvent .at-the extraction temperature, e. g., whenthe extraction is carried out at about. 250. .C. with a solution of mixed sodium salts .of organicacids, a pressure of Solvent to oilratiosfromol to l to as highas 10 or 15 to 1 maybe employed although the preferred rang is around 0.5 to 2 to 1. When appreciable amounts of esters are present solvent to--oil ratios greater. than 1' to .1 are-used, preferably 2 to 1- and .above,-if the extraction is being carried out at room temperature. When higher temperatures. are employed under these'circumstances the solvent to-oil ratio .is not so critical andratios as low as 0.5 to 1. may be used.

- The ratio of solvent 'to oil, strength-of aqueous salt solution, and the rate -of.flowzof the .oil phase are chosen when operating to hydrolyze-esters simultaneously in .sucha manner for: agiven length of extraction tower that part of-th-etower, preferably the lower part when the oil phase is traveling'up the tower, is employed for the selec- V tive extraction :of alcohols, acids .and carbonyls,

completely or in part, and the'top of the toweris then employed as a means for hydrolyzing :the esters and simultaneous extraction'of the acids and alcohols obtained from thehydrolysis of the esters.

It is, of :course, understood that this operation can be :carried out in two or-more extraction towers in series ;.that is, the first tower selectively extracts the acids, alcohols and: carbonyls nompletely or in part; andthe -oil phase containing the-:esters is'passed through a second or series of towers where it is contacted with an aqueous solution at the same or difierent temperature and pressure as the first tower to efiect the hydrolysis of esters and extraction of the acids and alcohols produced from the hydrolyzed esters to. obtain 6 per cent is superior to water at a pH of 8 or above. An advantage of using a pH of below 8, is that it is not necessary to keep adding fresh base to the extractant when recycling it in order to neutrala hydrocarbon free of all oxygenated compounds. ize the acid and, secondly, the use of mineral acid In order to assist in the extraction of acids to regenerate the organic acids from their salts from the feed mixture 2. little free base may be is not necessary since the extracted acids are in left in the salt solution. This removes the acids the free state and, therefore, can be stripped off. from the feed by neutralization. In this manner In speaking of the salt solution employed, it is thesolvent may be fortified or side streams of the to be understood that the solution is an aqueous resulting salt solution may be Withdrawn from solution. However, the aqueous salt solution the extraction tower and neutralized with minmay be modified by the addition thereto or a low eral acid to regenerate the organic acid. molecular weight water soluble aliphatic alcohol, If desired, the acids present in the oxy-comresulting in a mixed alcohol-aqueous salt solupound mixture may be removed completely or tion. Preferred alcohols to be used in such a partially by neutralization with causitc or other mixture are methyl alcohol and ethyl alcohol. neutralizing agent prior to extraction of the oxy- In order to demonstrate the efiectiveness of the compound mixture. Prior removal of the acids extraction process, the following examples are from the mixture has been found to exert a benecited: ficial eifect on the hydrolysis of esters contained 530 1 Example 1 therein, indicating, therefore, that the catalytic In Table I, there is Set forth the results e of hYdFOgeH lens Produced from the free tained by extracting a hydrocarbon synthesis oil, acid present n the feed is not as pronou as having a boiling range of to 350 C. and conthe hydlexyl 1011s from the Salt Solutlenstaining approximately 2.5 wt. per cent organic It has been found that the PH 0f the salt $0111- acids, calculated as C4 acid; 13.5 wt. per cent tien'empleyed in the Fraction process is a P alcohols, calculated as C4 alcohol; 7% carbonyl trolling variable afiecting thfi results Obtained. compounds calculated as carbonyl and 3 3 wt f the Sa1t S01uti0I1 s a D greaterfhan the per cent esters, calculated as C4 ester. The exelganlc aelqs extracted are f j 1n theferm tractions were carried out at room temperatures, e Sedlum e Tlle addltlen of a e employing various concentrations of sodium salt acid is then required to liberate the organic a solutions as indicated. The sodium salt solutions fIOm Its Selt- A P greater m 8 1S mamtelfled consisted of the stripped extract layers obtained y the pr s n e. of e base the Salt S0111t10nfrom the aqueous. caustic extraction of hydrocar- Whe the DH 0f he a 80111191011 s greater than bon synthesis oils and consisted of sodium salts 8, salt concentrations Of below about 30 Wt. per of acids whose average mglecular eight gun-ecent will produce an extractant of h h c p y sponded to about that of a C5 aliphatic acid}. The for ygenated compounds. data in Table I demonstrate that the salt solu- When employing a solution having a pH below tions are good extractants for oxygenated com- 8, salt concentrations of 30 wt. per cent or higher pounds, particularly alcohols. Data are also are required to obtain correspondingly high ca- 49 given showing the results obtained with water for pacities. If concentrations below about 30 wt. comparative purposes. per cent are employed at the lower pH values, Table I also emphasizes the influence of the pH the salt solution is inferior to water as an exof these salt solutions on their capacity for oxytractant. Any salt concentration above 5 wt. genated compounds.

TABLE I WihtP t0 td W'htP t0 td gipiirox. S cgmpofggl in Rgd fia te omp ii d Extfi' a c t 6 Ex eriment um Oil Olvent/ pH of CSalt Feed og Fgltract tr t i fi a 0 age Acid A513? gg Ester 'Acid g3? gg Ester -B 2 1.7 5.5 5.0 2.7 32 52.5 23.0 18.0 o 2 1.0 5.0 2.9 2.8 50 52.0 55.5 15.0 o 1 1.8 .8.3 4.5 .3.3 21.5 34.5 29.5 0.0 B 1 0.0 9.5 100.0 31.0 B 1 2.2 10.1 5 7 3.3 12.0 27.0 8.0 0.0 B 2 0.0 0.8 1.0 100.0 94.0 09.5 o 2 0.0 2.8 3.5 2.7 100.0 78.0 48.5 18.0 o 1 0.0 5.9 5.2 3.0 100.0 53.5 28.5 0.0 B 1 10.5 0.0 5.0 5.1 0.0 100.0 50.0 50.0 0.0 B 1 10.5 0.0 8.1 5.2 2.4 100.0 41.0 28.5 27.0 B 1 8.5 0.0 7.5 5.5 3.3 100.0 45.5 23.0 0.0 B 1 7.5 2.4 11.1 5.5 3.3 4.0 19.0 24.5 0.0 B 1 7.1 4.3 13.0 7.1 3.3 0.0 5.0 5.0 0.0 B 1 0.0 3.9 13.7 7.3 2.7 0.0 0.0 0.0 18.0 B 1 7.5 2.2 11.5 0.3 3.3 12.0 10.0 13.5 0.0 B 1 7.5 2.1 11.0 5.3 3.3 10.0 20.0 20.5 0.0 B 1 7.8 1.0 8.2 5.5 3.1 50.0 40.0 24.5 0.0

corresponding to a C5 aliphatic acid 1 Sodium salts derived from organic acids present in hydrocarbon synthesis oils, having an average molecular weight of that l Composition of Feed, Wt. Percent:

Acid as 0 Alcohol as C Carbonyl as C Ester as C Total Bomlggorange' B 2. 5 l3. 7 7. 3 3. 3 6. 8 207350 C 2. 3 l2. 7 6. 4 3. 3 24. 7 204350 b The pH was not determined but was approximately 10.5.

Increase in acid is due the pH. 4 1 1 to acid picked up from the ac ueous phase. Propionic acid had been added to salt solution to adjust hood of 100-350" appreciable hydrolysis of the esters present; in the oxygenated compounds-hydrocarbon mixture Bart of. the

, Example; 2

the'feed mixture. Corn- -and also the effect of the ysis. The data'indicate that cons'iderableportions of the ester present in the feed are hydrolyzedtoalcohols and acidswhich are subsequently recoveredin'the extract phase. It is not advisable tohavetoo muchfree acid presentdurin**thehydrolysis due-to the effect thereof on the pl-I of thesalt solution. If the acid builds up the pH of the salt solution drops, and When it reaches a-poi-nt near7.0 the rate of hydrolysis is appreciably loWe-reri. The build-up of acid can be avoided by continuously removing a portion of I the extraction mixture and; stripping the acid' therefrom.

Temperatures employed'during the extraction: hydrolysis operation should be in the neighbor- C., preferably 2 50-350 C. No

occurs at room' temperature. The hydrolysis rates. are extremely slw--at room temperature temperatures specifiedsbeing required.

showing the effect of the salt solution as comparedwith water as the hydrolysis medium, presence of free-organic acids duringthe hydrol- .evenat'the higher pH values, e. g. 10.5, the higher 30 Q 5,. between -.room, ;temperature and 350 10. .Under these conditions there are formed" an: extract phase, comprising-a solution of the oxygenated compounds in the salt solution and a rafiinate phase comprising. hydrocarbons. The phases are separated. Theoxygenated compounds'are recovered from the extract phase bykno'ivn means, such as fractional distillation or ,by sel vent extraction. Simple stripping of the oxygenated compounds from the extract by .fractional distillation is preferred. The oxygenated compounds will then. be recoyered,.usually1..in the vform of their water azeotropes. The solvent maybe. recycled to the system.

What is claimed is: v v

In a process for separating .preferentiallyoilsoluble organic oxygenated compoundsiroma predominantly hydrocarbon mixture comprising acids, esters and atleast one preferentially-oilsoluble organic oxygenated compound selected from the groupconsisting of alcohols, aldehydes, andketones,:the steps which comprise contacting said hydrocarbon'mixture at a' temperature :in' the range of 250 .C. and 350 C. withan. aqueous extraction solution containing a salt of a preferentially oil-soluble 'carboxylic acid having 3 to "12 "carbon atoms in the molecule, whereby the esters contained ins'aid mixture are hydrolyzed to acids and alcohols, and stratifying and separating an TABLE II [Batch hydrolysis of esters present in '25200 C(bpilm range gasoline fraction at 250 C. and 66 atm. gage pressure} Oxygcnated compounds s cretes Extracted by yg I R ti Hydrolysis g k I 3 Oon- Moi Per- Medium, M01 m Hydoly' tact cent Ester Percent Percent Run No. Gasoline Fraction Hydxoly'sis'Medium ;sis MedJ r' fiydrm 1 Egg? in Min lyzcd.

H S 13 t A d y ros ers ci s as lyzed Aclds (as Cs) butyric) Esters 464-125 Acids present 2.0 9.180 22.0 464-159... d0 2. 0 60 20. 0 4 4.149 2. 0 c 180 17.0 2.0 c 180 58. 5 03. 0 0.31 ,2. 0 60 47.0 63.0 0.26 2.0 60 11.0 63. 0 1.60 2.0 60 +16. 0 i 61. 0 1 90. 0 0.72 l. 70 2. 0 60 57. 0 45. 0 80. 0 0. 19 0. 31 2.0 .830 +13.0 13.0 57.0 0.23' (1.40 2. 0 a 30 V 59. 0 18.0 57.0 0.08 0. 24 2. 0 s 56. 6 14. 0 57. 0 0. 08 0.30 2. 0 8 10 52. 5 18.0 '57. 0 0.11 0.27 2.2 B 5 43.0 17.0 63.0 0.10 0.22 0.7 s 42. 8 4.0 33. 0 0.08 0. 4.0 30 62. 0 38.0 ,80. 0 0. .06 0.17 2.0 z 10 25.0 5. 0 53. 0 0. O0 0:12 2. 0 1230 45.0 31.0 40.0 0. 09 0.09 2. 0 B 30 47. 0 27.0 65.0 0. 10 0; 47 518-117 l. do I 2.0 B 30 15.0 5.0 62.0 0. 04 0.41

hydrocarbon phase.

11 Run made at 200 C. and 900 lbs/sq. in. gage pressure.

contact times do not includell hours required to bring about 2.0 wt. percent ester as Cq. approximately2 N aqueous causticat roomtemperature. Ester content remained essentially the same.

bomb containing hydrolysis medium and hydrocarbon deed of the alcohols and, about 3 5%, o fthe carbonyls.

Bomb containing hydrolysis medium was heated to 250 0. prior to introducing i Feed consisted of acid-free oil-boiling rangc'25" O. to about 400 C. Ester content about 1.3 wt. percent as Ga.

tower atapoint -near.-the--m-idsection thereof andycontacted, preferably countercurrently by an aqueous solution of a salt of at least one "organic-acid of 3 to about'12 carbon-atoms at a temperature between the freezing point of the g V solvent and the critical temperature, preferably 75 2,494,371

70.0 incl-percent of-aclds c xtracted with watcrat250 0. prior to hydrolysisrim.

aqueous extract vcontaining saidv preferentially 1 oil-soluble organic oxygenated compounds.

References Cited in the file of this patent UNITED STATES PA'I'ENTS Number Name... Date 2,274,750 Soenksenetal. Mar. 3, 1942 2,452;121 Grahame Oct. 26, 1948 -2;,470,7'82 McGrath et al. :May 24, 1949 Wadley ..1Jan. 10, 1950 

